EP1394158B1 - Thiophen Derivate und entsprechende optische Elemente - Google Patents

Thiophen Derivate und entsprechende optische Elemente Download PDF

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EP1394158B1
EP1394158B1 EP03019529A EP03019529A EP1394158B1 EP 1394158 B1 EP1394158 B1 EP 1394158B1 EP 03019529 A EP03019529 A EP 03019529A EP 03019529 A EP03019529 A EP 03019529A EP 1394158 B1 EP1394158 B1 EP 1394158B1
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group
compound
alkyl group
carbon atoms
substituent
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EP1394158A1 (de
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Ryo Nishio
Naoyuki Nishikawa
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Fujifilm Corp
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    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only
    • G11B7/245—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only containing a polymeric component
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
    • C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/24—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/30—Hetero atoms other than halogen
    • C07D333/32—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
    • G11B7/24—Record carriers characterised by shape, structure or physical properties, or by the selection of the material
    • G11B7/241—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material
    • G11B7/242—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers
    • G11B7/244—Record carriers characterised by shape, structure or physical properties, or by the selection of the material characterised by the selection of the material of recording layers comprising organic materials only

Definitions

  • the present invention relates to a novel compound which is useful as an electro-optical material or a non-linear optical material used in the field of opto-electronics and photonics.
  • the invention also relates to various kinds of optical elements such as phase difference plate and electro-optical devices, which utilize non-linear optical effect.
  • non-linear optical materials search for new materials and device production have been made mainly in the realm of inorganic non-linear optical materials.
  • organic non-linear optical materials have attracted attention for their following properties: (1) large optical non-linearity, (2) quick response, (3) high threshold value for optical damages, (4) capability of versatile molecular design, and (5) excellent production adaptability.
  • Development for the secondary non-linear optical effect requires that polarization induced by electric fields should have no centro symmetricity. Accordingly, it is necessary to arrange molecules showing non-linear optical effect or groups having non-linear optical response in such a structure that lacks centro symmetricity in the material.
  • the present invention is to solve the foregoing problems in the related art and attain the following objects. That is, the invention intends to provide (1) a novel compound that is useful as a non-linear optical material comprising an organic material with no or controlled orientation relaxation, (2) a novel compound which is useful as a non-linear optical material that forms second harmonic waves upon orientation in electric fields, and (3) an optical element, a non-linear optical material, and an electro-optical material using a crosslinked or non-crosslinked body of the compound.
  • a first aspect of the invention provides a compound represented by the following general formula (I):
  • -Ar 2 -A-S 2 -P 2 substitutes on the 4-position or 5-position of a thiophene ring.
  • Ar 1 and Ar 2 each independently represent a single bond, an aromatic ring having 5 to 14 carbon atoms, or a biphenyl group, provided that at least one of Ar 1 and Ar 2 represents one of a naphthalene ring and a biphenyl group that may have a substituent.
  • D represents an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or a substituent represented by P 1 -S 1 -, or an amino group having a cyclic structure.
  • A represents an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO 2 -), and a sulfonyloxy group (-SO 3 -).
  • S 1 and S 2 each independently represent a bivalent linking group.
  • P 1 and P 2 each independently represent a substituent consisting of atoms selected from C, H, O, N, S, and a halogen atom, and at least one of P 1 and P 2 represents a polymerizable group including an acryloyloxy group or a methacryloyloxy group.
  • the thiophene ring may have a substituent.
  • a second aspect of the invention provides an optical element containing the compound of the first aspect or a polymer of the compound.
  • a third aspect of the invention provides a non-linear optical material or an electro-optical material, containing the compound of the first aspect or a polymer formed by polymerizing the compound.
  • a fourth aspect of the invention provides a compound represented by the following general formula (I-A):
  • -Ar 2 -P 4 substitutes on the 4-position or 5-position of a thiophene ring.
  • Ar 1 and Ar 2 each independently represent a single bond, an aromatic ring having 5 to 14 carbon atoms, or a biphenyl group, provided that at least one of Ar 1 and Ar 2 represents one of a naphthalene ring and a biphenyl group that may have a substituent.
  • P 6 represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms wherein one or more of-CH 2 - in the alkyl group may be
  • D 1 represents one selected from the group consisting of an oxygen atom (-O-), a sulfur atom (-S-), and -NP 5 -.
  • P 5 may be independent of P 3 or bonded with P 3 to form a ring.
  • the thiophene ring may have a substituent.
  • a fifth aspect of the invention provides an optical element containing the compound of the fourth aspect or a polymer thereof.
  • a sixth aspect of the invention provides a non-linear optical material or an electro-optical material, containing the compound of the fourth aspect or a polymer formed by polymerizing the compound.
  • novel compound of the present invention is represented by the following general formula (I):
  • Ar 1 and Ar 2 each independently represent a single bond, an aromatic ring having 5 to 14 carbon atoms, or a biphenyl group, provided that at least one of Ar 1 and Ar 2 represents one of a naphthalene ring and a biphenyl group that may have a substituent.
  • D represents an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or a substituent represented by P 1 -S 1 -, or an amino group having a cyclic structure.
  • A represents an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO 2 -), and a sulfonyloxy group (-SO 3 -).
  • S 1 and S 2 each independently represent a bivalent linking group.
  • P 1 and P 2 each independently represent a substituent consisting of atoms selected from C, H, O, N, S, and a halogen atom, and at least one of P 1 and P 2 represents a polymerizable group.
  • the thiophene ring may have a substituent.
  • Ar 1 or Ar 2 in general formula (I) is preferably an aromatic ring having 5 to 14 carbon atoms (a ring having aromaticity including a hetero ring having 5 or more carbon atoms) or a biphenyl group, and more preferably a benzene ring, a naphthalene ring or a biphenyl group. It is particularly preferred that one of Ar 1 and Ar 2 is a naphthalene ring. Specifically, it is particularly preferred that Ar 1 is a benzene ring and Ar 2 is a naphthalene ring, or Ar 1 is a naphthalene ring and Ar 2 is a benzene ring.
  • Ar 1 or Ar 2 represents an aromatic ring having a substituent
  • substituents include lower alkyl groups having 1 to 6 carbon atoms and, more preferably, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group and hexyl group.
  • D in general formula (I) is an oxygen atom (-O-), a sulfur atom (-S-), -NH- as an electron donating group, a substituted amino group (-NR-) in which R is preferably a substituent of a lower alkyl group having 1 to 6 carbon atoms, or a substituent represented by P 1 -S 1 -, and R is particularly preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl, a hexyl group, or the like, or an amino group having one of the following cyclic structures: D is particularly preferably an oxygen atom.
  • A represents an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO 2 -), and a sulfonyloxy group (-SO 3 -).
  • A is preferably an ester group (-COO-) or a sulfonyloxy group (-SO 3 -).
  • the linking groups represented by S 1 and S 2 in general formula (I) have preferably 2 to 12 carbon atoms, and more preferably 4 to 8 carbon atoms. Further, S 1 and S 2 may also have a cyclic structure and a cyclohexyl ring is preferred when having the cyclic structure.
  • Examples of linking groups include an alkylene group.
  • the linking group may have one or plural substituents. In this case, examples of the substituents include a substituent having 1 to 4 carbon atoms and a halogen atom. Particularly preferred are a methyl group, an ethyl group, a propyl group and an isopropyl group.
  • the carbon atom having the substituent is an asymmetric carbon, the steric arrangement thereof may be R, S, or a mixture thereof at an arbitrary rate.
  • P 1 and P 2 in general formula (I) each independently represent a substituent consisting of atoms selected from C, H, O, N, S, and a halogen atom. At least one of P 1 and P 2 represents a polymerizable group including an acryloyloxy group or a methacryloyloxy group. Only one of P 1 and P 2 may be a polymerizable group but it is preferred that both P 1 and P 2 are polymerizable groups.
  • novel compound of the present invention may be represented by the following general formula (I-A):
  • Ar 1 and Ar 2 have the same meaning as descried in general formula (I).
  • the thiophene ring may have a substituent.
  • D 1 examples include -O-, -NP 3 -, -NR- in which R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, or a hexyl group, or an amino group having one of the following cyclic structures: D 1 is particularly preferably -O-, -NP 1 -, or -NR- in which R represents a methyl group, an ethyl group, a propyl group, or an isopropyl group.
  • P 3 in general formula (I-A) represents a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms.
  • P 3 may have a substituent consisting of atoms selected from C, H, O, N, S, and a halogen atom.
  • P 3 examples include a linear, branched or cyclic alkyl group wherein one or more hydrogen atom(s) at an arbitrary position may also be substituted with a halogen atom, a polyethyleneoxy group, or the following polymerizable substituent (q is an integer):
  • q is preferably 2 to 14, more preferably 2 to 10, and still more preferably 4 to 10.
  • P 3 is particularly preferably a linear or branched alkyl group having 1 to 14 carbon atoms, and further preferably a linear alkyl group having 1 to 12 carbon atoms.
  • Examples of P 4 include the following substituent groups:
  • -P 4 in general formula (I-A) represents -P 4 '-P 6
  • the alkyl group may have a substituent consisting of atoms selected from C, H, O, N, S, and a halogen atom
  • -P 4 '- represents a bivalent electron attracting group consisting of atoms selected from the group consisting of an ester group (-COO-), a sulfonyl group (-SO 2 -), and a sulfoxy group (-SO 3 -).
  • Examples of P 6 include a linear, branched or cyclic alkyl group (one or more hydrogen atom(s) at an arbitrary position may be substituted with a halogen atom), a polyethyleneoxy group, and the following polymerizable substituent groups (q is an integer):
  • q is preferably 2 to 14, more preferably 2 to 10, and further preferably 4 to 10.
  • P 4 ' examples include an ester group (-COO-), a sulfonyl group (-SO 2 -), a sulfoxy group (-SO 3 -), or the following substituents:
  • Ar 1 , Ar 2 , D, A, S 1 , S 2 , P 1 , and P 2 have the same meanings as described above.
  • Examples of the compound represented by general formula (I) include the following compounds.
  • Examples of the compound represented by general formula (I-A) include the following compounds.
  • Ar 1 , Ar 2 , D, S 1 , S 2 , P 1 , and P 2 have the same meanings as described above and L represents a leaving group and Y represents a protective group.
  • the compound represented by compounds A and B are used as the starting material and stirred in the presence of a Pd catalyst (Pd catalyst is, preferably, 0.1 to 5 mol% and, further preferably, 1 to 2 mol% based on the compound A) and the base I (base I is preferably 1 to 4 equivalent amount and, more preferably, 1 to 2 equivalent amount to the compound B) in an organic solvent under an overheating condition at about 50 to 150°C for several hours, a compound represented by the compound C can be obtained.
  • a Pd catalyst is, preferably, 0.1 to 5 mol% and, further preferably, 1 to 2 mol% based on the compound A
  • base I base I is preferably 1 to 4 equivalent amount and, more preferably, 1 to 2 equivalent amount to the compound B
  • Examples of the protective group Y in the compound A include tert-butoxycarbonyl (Boc) group, benzoylcarbonyl (Cbz) group, acetyl (Ac) group or the like, for example, when D is an amino group.
  • D is other substituent than described above, protecting and deprotecting can be conducted in accordance with the method as described in Protective Groups in Organic Chemistry, Plenum Press (London and New York, 1973); Green, T. W., Protective Groups in Organic Synthesis, Wiley New York, 1981; and Peptides, Vol. I, Schrooder and Lubke, Academic Press (London and New York, 1965).
  • Examples of the Pd catalyst used in the reaction are preferably, Pd(PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , Pd(OAc) 2 -PPh 3 , and Pd 2 (dba) 3 CHCl 3 -PPh 3 .
  • base I inorganic and organic bases can be used and preferred examples of the base may include potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium acetate, sodium acetate and sodium phosphate.
  • organic solvent to be used examples include N,N-dimethylformamide (DMF), N,N-dimethylacetoamide (DMA), tetrahydrofuran (THF), chloroform, dichloromethane and dimethylsulfoxide (DMSO).
  • DMF N,N-dimethylformamide
  • DMA N,N-dimethylacetoamide
  • THF tetrahydrofuran
  • chloroform dichloromethane
  • DMSO dimethylsulfoxide
  • the base II in which the base II is preferably 1 to 2 equivalent amount, and further preferably 1 to 1.2 equivalent amount to the compound C
  • B(OEt) 3 is dropped and stirred at a room temperature for several hours
  • a boronic acid compound represented by the compound D is obtained.
  • Preferred examples of the base II include tert-butyl lithium, n-butyl lithium, lithium diisopropylamide (LDA), sodium hydride, lithium hydride and potassium carbonate and, particularly preferably, include tert-butyl lithium, n-butyl lithium and lithium diisopropylamide (LDA).
  • Preferred base III may include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and lithium hydroxide.
  • Preferred examples of the leaving group L include halogen atom, alkyl sulfonyloxy group or arylsulfonyloxy group.
  • Ar 1 , Ar 2 and D have the same meanings as described above, L represents a leaving group, Y represents a protective group, S represents a spacer, and P represents a polymerizable group.
  • Examples of the protective group Y in the compound J include tert-butoxycarbonyl (Boc) group, benzoylcarbonyl (Cbz) group, acetyl (Ac) group or the like, for example, when D is an amino group.
  • Boc tert-butoxycarbonyl
  • Cbz benzoylcarbonyl
  • Ac acetyl
  • protecting and deprotecting can be conducted in accordance with the method as described in "Protective Groups in Organic Chemistry Journal".
  • Examples of the Pd catalyst used in the reaction are preferably, Pd(PPh 3 ) 4 , PdCl 2 (PPh 3 ) 2 , Pd(OAc) 2 -PPh 3 , and Pd 2 (dba) 3 CHCl 3 -PPh 3 .
  • base I inorganic and organic bases can be used and preferred examples of the base may include potassium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium acetate, sodium acetate and sodium phosphate.
  • organic solvent to be used examples include N,N-dimethylformamide (DMF), N,N-dimethylacetoamide (DMA), tetrahydrofuran (THF), chloroform, dichloromethane and dimethylsulfoxide (DMSO).
  • DMF N,N-dimethylformamide
  • DMA N,N-dimethylacetoamide
  • THF tetrahydrofuran
  • chloroform dichloromethane
  • DMSO dimethylsulfoxide
  • the compound L is stirred under the presence of the base II (in which the base II is, preferably, 1 to 2 equivalent amount, further preferably, 1 to 1.2 equivalent amount to the compound L) at a low temperature of 0°C or lower for several hours and then B(OEt) 3 is dropped and stirred at a room temperature for several hours, a boronic acid compound represented by the compound M is obtained.
  • the base II include tert-butyl lithium, n-butyl lithium, lithium diisopropylamide (LDA), sodium hydride, lithium hydride and potassium carbonate and, particularly preferably, include tert-butyl lithium, n-butyl lithium and lithium diisopropylamide (LDA).
  • Preferred base III may include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and lithium hydroxide.
  • Preferred examples of the leaving group L include halogen atom, alkyl sulfonyloxy group or arylsulfonyloxy group.
  • the optical element as the application use of the compound represented by general formula (I) of the invention may include functional films (for example, optical films, ferroelectric films, anti-ferroelectric films, and piezoelectric films) and functional devices (for example, non-linear optical devices, electro-optical devices, pyroelectric devices, piezoelectric devices and optical modulation devices) utilized in the optical field and the electronics field.
  • functional films for example, optical films, ferroelectric films, anti-ferroelectric films, and piezoelectric films
  • functional devices for example, non-linear optical devices, electro-optical devices, pyroelectric devices, piezoelectric devices and optical modulation devices
  • non-linear optical devices electro-optical devices
  • a wave guide type device is prepared, for example, as described in "Optical Wave Optics", issued from Corona Co., (1998), page 200, which is then utilized as an optical modulator for modulating the phase or intensity of optical waves or optical switch.
  • JP-A No. 9-22035 discloses an example for the use
  • the aimed compound S is obtained (compound represented by P 3 -L is, preferably, 1 to 2 equivalent amount, more preferably, 1 to 1.3 equivalent amount to the compound R by the equivalent amount ratio).
  • Preferred examples of the base III include sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate and lithium hydroxide.
  • Preferred examples of the leaving group L may include halogen atom, alkyl sulfonyloxy group or arylsulfonyloxy group.
  • the organic solvent used in the schemes 1 and 2 can be utilized.
  • an optical element of the invention include functional films (for example, optical films, ferroelectric films, anti-ferroelectric films, piezoelectric films) and functional devices (for example, non-linear optical devices, electro-optical devices, pyroelectric devices, piezoelectric devices and optical modulation devices) utilized in the field in the optical field or electronics field.
  • functional films for example, optical films, ferroelectric films, anti-ferroelectric films, piezoelectric films
  • functional devices for example, non-linear optical devices, electro-optical devices, pyroelectric devices, piezoelectric devices and optical modulation devices
  • the non-linear optical material and the electro-optical material of the invention contain the compound of the invention, as at least one constituent component, or otherwise contain a polymer polymerized from the compound of the invention, as at least one constituent component.
  • the polymer polymerized from the compound of the invention may be used as a non-linear optical material and an electro-optical material.
  • the non-linear optical material and the electro-optical material of the invention include two embodiments. One is an embodiment in which the non-linear optical material and the electro-optical material are made of the compound of the invention alone. The other is an embodiment in which the non-linear optical material and the electro-optical material are made of the compound of the invention and a medium. The producing methods thereof will be shown below.
  • the non-linear optical material and the electro-optical material of the invention can be produced by (1) coating or sandwiching a monomer composition containing the compound of the invention to a support or the like; (2) orienting the same; and (3) crosslinking the same while applying an orientation treatment.
  • the compound of the invention preferably has a crosslinking substituent.
  • the material can be produced by (1) dissolving a composition containing the compound of the invention and a polymeric medium supporting the same, or a composition containing a polymer of the compound of the invention into a solvent; (2) coating or sandwiching the same to a support followed by drying; and (3) applying an orientation treatment.
  • the polymeric medium is not particularly limited.
  • acrylic polymer such as PMMA
  • imide type polymer such as fluoropolyimide and polyarbonate.
  • the solvent to be used is not particularly limited. Examples thereof include ester type solvent such as ethyl acetate, ketone type solvent such as methyl ethyl ketone, ether type solvent such as tetrahydrofuran and halogen type solvent such as chloroform and dichloromethane, as well as mixed solvents thereof.
  • a method of disposing a layer containing a compound having a non-linear optical responsive group (a portion represented by D-Ar 1 -thiophene ring-Ar 2 -A in general formula (I) or D 1 -Ar 1 -thiophene ring-Ar 2 -P 4 in general formula (I-A)) as at least a portion of the constituent component on a substrate, a well-known method is adopted.
  • the substrate include transparent substrates such as glass, polymeric film or reflection plate, and a transparent electrode layer or insulation film may also be disposed optionally on the substrate.
  • a transparent electrode may or may not be provided but ITO vapor deposited on the substrate is preferred, with no particular restriction thereto.
  • the insulation film may or may not be provided and an insulation film of polyimide type or polyvinyl alcohol is preferred when the insulation film is provided. Further, in a case of using a case of using a pair of substrates, spacer, sealant and the like may be used optionally.
  • a known method may be adopted for coating, and examples of the coating method include curtain coating, extrusion coating, roll coating, spin coating, dip coating, bar coating, spray coating, slide coating and printing coating.
  • the molecules are oriented by applying external electric fields or external magnetic fields.
  • a method of using the external electric fields is preferred and use of contact poling method (plain electrode poling method, electrode sandwich poling method) or corona poling method is preferred.
  • the polymer comprising the compound as one of the constituent components can be prepared by the following methods, which should not be construed to limit the scope of the invention.
  • various known crosslinking methods suitable to introduced crosslinkable substituents can be adopted.
  • the crosslinkable substituent is an acryloyloxy group or methacryloyloxy group
  • radical polymerization of using a radical initiator such as AIBN in an organic solvent is particularly preferred.
  • the compound of the invention has a liquid crystal property.
  • application of the external electric fields or external magnetic fields is conducted preferably within a temperature range showing the liquid crystal phase.
  • a method of heating to an isometric phase under the application of external electric fields or external magnetic fields and then cooling the same to a liquid crystal phase is also preferred.
  • an appropriate intensity for the orientation control of liquid crystal molecules is used.
  • an appropriate polymerization initiator, polymerization inhibitor, photosensitizer, crosslinker, liquid crystal orientation aid, etc. may be added as required.
  • Figs. 1 and 2 to be described below show typical examples of a layer structure for the non-linear optical material in the invention.
  • a non-linear optical response layer 1 an insulation film 2, and a transparent electrode substrate 3.
  • a first embodiment of the invention provides a compound represented by the following general formula (I):
  • -Ar 2 -A-S 2 -P 2 substitutes on the 4-position or 5-position of a thiophene ring.
  • Ar 1 and Ar 2 each independently represent a single bond, an aromatic ring having 5 to 14 carbon atoms, or a biphenyl group, provided that at least one of Ar 1 and Ar 2 represents one of a naphthalene ring and a biphenyl group which may have a substituent.
  • D represents an oxygen atom (-O-), a sulfur atom (-S-), a substituted amino group (-NR-) in which R represents a hydrogen atom, a lower alkyl group having 1 to 6 carbon atoms, or a substituent represented by P 1 -S 1 -, or an amino group having a cyclic structure.
  • A represents an electron attracting group selected from an ester group (-COO-), a sulfonyl group (-SO 2 -), and a sulfonyloxy group (-SO 3 -).
  • S 1 and S 2 each independently represent a bivalent linking group.
  • P 1 and P 2 each independently represent a substituent consisting of atoms selected from C, H, O, N, S, and a halogen atom. At least one of P 1 and P 2 represents a polymerizable group.
  • the thiophene ring may have a substituent.
  • a second embodiment of the invention provides the compound of the first embodiment, wherein Ar 1 represents a benzene ring and Ar 2 represents a naphthalene ring; or Ar 1 represents a naphthalene ring and Ar 2 represents a benzene ring.
  • a third embodiment of the invention provides the compound of the first or second embodiment, wherein S 1 and S 2 each independently represent an alkylene group having 2 to 12 carbon atoms.
  • a fourth embodiment of the invention provides the compound of any one of the first to third embodiments, wherein P 1 and P 2 each independently represent an acryloyloxy group or a methacryloyloxy group.
  • a fifth embodiment of the invention provides an optical element containing the compound of any one of the first to fifth embodiments or a polymer of the compound.
  • a sixth embodiment of the invention provides a non-linear optical material containing the compound of any one of the first to fifth embodiments, or a polymer formed by polymerizing the compound, as at least one constituent component.
  • An seventh embodiment of the invention provides an electro-optical material containing the compound of any one of the first to fifth embodiments, or a polymer formed by polymerizing the compound, as at least one constituent component.
  • a eighth embodiment of the invention provides a compound represents by the following general formula (I-A):
  • Ar 1 and Ar 2 have the same meaning as descried in general formula (I).
  • -Ar 2 -P 4 substitutes on the 4-position or 5-position of a thiophene ring.
  • P 6 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms wherein one or more of -CH 2 - in the alkyl group may be replaced with
  • the thiophene ring may have a substituent.
  • a tenth embodiment of the invention provides the compound of the ninth embodiment, wherein Ar 1 is a 1,4-phenylene group and Ar 2 is 2,6-naphthalene group; or Ar 1 is a 2,6-naphthalene group and Ar 2 is a 1,4-phenylene group.
  • a eleventh embodiment of the invention provides the compound of the eleventh or twelfth embodiment, wherein P 3 and P 5 each independently represent a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms.
  • a twelfth embodiment of the invention provides an optical element containing the compound of the ninth to thirteenth embodiments or a polymer of the compound.
  • a thirteenth embodiment of the invention provides a non-linear optical material containing the compound of any one of ninth to thirteenth embodiments, or a polymer formed by polymerizing the compound, as at least one constituent component.
  • a fourteenth embodiments of the invention provides an electro-optical material containing the compound of any one of ninth to thirteenth embodiments, or a polymer formed by polymerizing the compound, as at least one constituent component.
  • 5-(4-methoxy-phenyl)-thiophene-2-boronic acid (5.42 g, 23.2 mmol) and 6-bromo-naphthalene-2-carboxylic acid methyl ester (6.15 g, 23.2 mmol) were dissolved in 65 ml of dimethylformamide (DMF) and stirred under the presence of Pd(PPh 3 ) 4 (266 mg, 0.23 mmol) and potassium carbonate (9.60 g, 69.6 mmol) at 80°C for 12 hours. Then, 150 ml of water was added and extracted with ethyl acetate.
  • DMF dimethylformamide
  • 6-[5-(4-methoxy-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid methyl ester (4.10 g, 10.9 mmol) was dissolved in 85 ml of dichloromethane, to which 21.8 ml of 1.0 mol/L dichloromethane solution of boron tribromide (BBr 3 ) was dropped under ice cooling and then stirred at a room temperature for 4 hours. Then, water was added to the reaction solution, and resultant precipitates were filtered and washed with water to obtain 3.80 g of 6-[5-(4-hydroxy-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid.
  • BBr 3 boron tribromide
  • Acrylic acid 2-hydroxy-ethyl ester (20 g, 172 mmol) and triethylamine (34.8 g, 344 mmol) were dissolved in 250 ml of THF, and methane sulfonyl chloride (23.6 g, 206 mmol) was gradually dropped to the mixed solution.
  • 250 ml of water was added, extracted with ethyl acetate and washed with an aqueous saturated solution of sodium chloride. Then, extracted solution was dried on anhydrous magnesium sulfate and the solvent was distilled off to obtain a compound: acrylic acid 2-methanesulfonyloxy-ethyl ester represented by P-S-L in the scheme 2.
  • 6-[5-(4-hydroxy-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid (200 mg, 0.577 mmol) and acrylic acid 2-methanesulfonyloxy-ethyl ester (449 mg, 2.31 mmol) were heated in 5 ml of dimethylformamide under the presence of potassium carbonate (478 mg, 3.46 mmol) at 80°C and stirred for 8 hours. Then, water was added to the reaction solution, extracted with ethyl acetate and the extracted solution was washed with an aqueous saturated solution of sodium hydrogen carbonate and an aqueous saturated solution of sodium chloride.
  • C represents the crystal
  • N represents the nematic phase
  • S represents the smectic phase
  • I represents the isometric phase.
  • 6-[5-(4-hydroxy-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid 6-acryloyloxy-hexyl ester (1.73 g, 3.46 mmol) and acrylic acid 4-methanesulfonyloxy-butyl ester (1.53 g, 6.92 mmol) were heated in dimethylformamide under the presence of potassium carbonate (1.43 g, 10.4 mmol) at 80°C and stirred for 5 hours. Then, water was added to the reaction solution, extracted with ethyl acetate and the extracted solution was washed with an aqueous saturated solution of sodium hydrogen carbonate and an aqueous saturated solution of sodium chloride.
  • 6- ⁇ 5- ⁇ 4-(acetyl-methyl-amino)-phenyl]-thiophen-2-yl ⁇ -naphthalene-2-carboxylic acid methyl ester (4.3 g, 10.3 mmol) were dissolved in 100 ml of dimethyl sulfoamide, to which 10 ml of 5.0 N hydrochloric acid and 20 ml of water were added and stirred at 80°C for 12 hours. Then, water was added to the reaction solution and precipitates were separated by filtration.
  • 6-[5-(4-methylamino-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid (1.00 g, 2.78 mmol) and acrylic acid 2-methanesulfonyloxy-hexyl ester (2.78 g, 11.1 mmol) were heated at 80°C in 1 ml of dimethylformamide under the presence of potassium carbonate (2.30 g, 16.7 mmol) and stirred for 10 hours. Then water was added to the reaction solution, and extracted with ethyl acetate and the extracted solution was washed with an aqueous saturated solution of sodium hydrogen carbonate and an aqueous saturated solution of sodium chloride.
  • N-(4-bromo-phenyl)-N-methyl-acetamide was replaced with N-(4-bromo-phenyl-acetamide, and 6-[5-(4-acetylamino-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid methyl ester was synthesized in accordance with the method of Synthesis Example 9.
  • 6-[5-(4-acetylamino-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid methyl ester (1.5 g, 3.74 mmol) was dissolved in 30 ml of dimethylformamide, to which 5 ml of 5.0 N hydrochloric acid and 15 ml of water were added and stirred at 100°C for 24 hours. Then, water was added to the reaction solution and resultant precipitates were separated by filtration.
  • 6-[5-(4-amino-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid (0.6 g, 1.73 mmol) and acrylic acid 6-methanesulfonyloxy-hexyl ester (2.6 g, 10.4 mmol) were heated at 80°C in 10 ml of dimethylformamide under the presence of potassium carbonate (1.43 g, 10.4 mmol) and stirred for 12 hours. Then water was added to the reaction solution and extracted with ethyl acetate, and the extracted solution was washed with an aqueous saturated solution of sodium hydrogen carbonate and an aqueous saturated solution of sodium chloride.
  • 6-[-5-(4-hydroxy-2-methyl-phenyl)-thiophen-2-yl]-naphthalene-2-carboxylic acid obtained (1.4 g, 3.9 mmol) and methanesulfonic acid decyl ester (2.76 g, 11.7 mmol) were heated to 70°C in 20 ml of dimethyl formamide under the presence of potassium carbonate (2.1 g, 15 mmol) and stirred for 10 hours. Then, water was added to the reaction solution and extracted with ethyl acetate, and the extracted solution was washed with an aqueous saturated solution of sodium hydrogen carbonate and an aqueous saturated solution of sodium chloride.
  • a constituent material comprising 6- ⁇ 5-[4-(4-acryloyloxy-butoxy)phenyl]-thiophen-2-yl ⁇ -naphthalene-2-carboxylic acid 4-acryloyloxy-butyl ester (compound 2) (92.7 parts by weight), phenothiazine (1.3 parts by weight), a polymerization initiator (Illugacure 651, trade name of products manufactured by Ciba Guigy) (4 parts by weight) and hydroquinone monomethyl ether (2 parts by weight) was sandwiched in a horizontally oriented cell having a 4 ⁇ m gap and comprising a glass substrate having ITO transparent electrode portions formed by coating a polyimide thin film as an insulation film (manufactured by E. H. I). Then, the obtained sample was kept at 160°C while applying a DC voltage at 200 V across transparent electrodes, and UV irradiation (254 nm, 10 W/cm, 3 min) was conducted.
  • Infrared light of YAG laser (1.6 ⁇ m) was irradiated to the sample obtained as described above to confirm generation of second harmonic waves.
  • the intensity of the second harmonic waves of the sample was maintained for one month.
  • a chloroform solution comprising 6- ⁇ 5-[4-(4-acryloyloxy-butoxy)-phenyl]-thiophen-2-yl ⁇ -naphthalene-2-carboxylic acid 4-acryloyloxy-butyl ester (compound 2) (92.7 parts by weight), phenothiazine (1.3 parts by weight), a polymerization initiator (Illugacure 651, trade name of products manufactured by Ciba Guigy Co.) (4 parts by weight), and hydroquinone monomethyl ether (2 parts by weight) was coated by spin coating (1000 rpm, 20 sec) on a glass substrate having ITO transparent electrode portions formed by coating a polyimide film as an insulation film and then dried under a reduced pressure for 12 hours.
  • the obtained sample was kept at 160°C and voltage was applied by using a corona poling method (application voltage: 5.0 kV, 20 min) and then UV irradiation (254 nm, 10 W/cm, 3 min) was conducted while applying the voltage.
  • An aluminum electrode was carried on a crosslinked non-linear optical response portion by vapor deposition to manufacture a non-linear optical material having electrodes on both ends.
  • Infrared light of YAG laser (1.06 ⁇ m) was irradiated to the sample obtained as described above to confirm the generation of second harmonic waves and the electro-optical effect.
  • the intensity of the second harmonic waves and the electro-optical effect of the sample were maintained for one month.
  • Fig. 3 shows the intensity of the second harmonic waves before and after corona poling for the sample obtained as described above.
  • crosslinkable compound of the invention is useful as an organic non-linear optical material with remarkably suppressed aging decay for the electro-optical effect or generation of second harmonic waves.
  • the compound 23 was sandwiched in a horizontally oriented cell having 5 ⁇ m gap and comprising a glass substrate with an ITO transparent electrode portion (manufactured by E. H. I). Then, the obtained sample was kept at 70°C while applying a DC voltage at 150 V across the transparent electrodes. An infrared light of YAG laser (1.06 ⁇ m) was irradiated to the obtained sample to confirm the generation of second harmonic waves.
  • Fig. 4 shows the intensity of the second harmonic waves for the sample obtained as described above and for the sample of 5CB for reference use oriented under electric fields under the same conditions.
  • the non-linear optical compound of the invention has higher non-linear optical characteristics than the rod-like liquid crystal compound 5CB (compound for reference) in a state of electric field orientation and it is useful as an organic non-linear optical material.
  • the present invention can provide (1) a novel compound which is useful as a non-linear optical material comprising an organic material with no or controlled orientation relaxation, (2) a novel compound which is useful as a non-linear optical material that generates second harmonic waves upon electric field orientation and (3) an optical element, a non-linear optical material and an electro-optical material using the crosslinked product or non-crosslinked product of the compound.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Modulation, Optical Deflection, Nonlinear Optics, Optical Demodulation, Optical Logic Elements (AREA)
  • Heterocyclic Compounds Containing Sulfur Atoms (AREA)
  • Investigating Or Analysing Biological Materials (AREA)
  • Luminescent Compositions (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (12)

  1. Verbindung, die durch die folgende allgemeine Formel (I) dargestellt wird:
    Figure imgb0068
     wobei:
    -Ar2-A-S2-P2 die 4-Position oder 5-Position eines Thiophenrings substituiert;
    Ar1 und Ar2 jeweils unabhängig voneinander eine Einfachbindung, einen aromatischen Ring mit 5 bis 14 Kohlenstoffatomen oder eine Biphenylgruppe darstellen, unter der Voraussetzung, daß wenigstens eines von Ar1 und Ar2 eines aus einem Naphthalinring und einer Biphenylgruppe darstellen, die einen Substituenten aufweisen können;
    D ein Sauerstoffatom (-O-), ein Schwefelatom (-S-), eine substituierte Aminogruppe (-NR-), in der R ein Wasserstoffatom, eine niedere Alkylgruppe mit 1 bis 6 Kohlenstoffatomen darstellt, oder einen durch P1-S1- dargestellten Substituenten oder eine Aminogruppe mit einer cyclischen Struktur darstellen; und
    A eine elektronenanziehende Gruppe ausgewählt aus einer Estergruppe (-COO-), einer Sulfonylgruppe (-SO2-) und einer Sulfonyloxygruppe (-SO3-) darstellt;
    S1 und S2 jeweils unabhängig voneinander eine divalente Verbindungsgruppe darstellen;
    P1 und P2 jeweils unabhängig voneinander einen Substituenten bestehend aus Atomen ausgewählt aus C, H, 0, N, S und einem Halogenatom darstellen;
    wenigstens eines von P1 und P2 eine polymerisierbare Gruppe darstellen, die eine Acryloyloxygruppe oder eine Methacryloyloxygruppe einschließen; und
    der Thiophenring einen Substituenten aufweisen kann.
  2. Verbindung gemäß Anspruch 1, wobei:
    Ar1 einen Benzolring darstellt und Ar2 einen Naphthalinring darstellt; oder
    Ar1 einen Naphthalinring darstellt und Ar2 einen Benzolring darstellt.
  3. Verbindung gemäß Anspruch 1 oder 2, wobei S1 und S2 jeweils unabhängig voneinander eine Alkylengruppe mit 2 bis 12 Kohlenstoffatomen darstellen.
  4. Optisches Element umfassend die Verbindung gemäß einem der Ansprüche 1 bis 3 oder ein Polymer dieser Verbindung.
  5. Nichtlineares optisches Material umfassend als wenigstens einen Bestandteil die Verbindung gemäß einem der Ansprüche 1 bis 3 oder ein Polymer, das durch Polymerisieren der Verbindung gebildet wird.
  6. Elektrooptisches Material umfassend als wenigstens einen Bestandteil die Verbindung gemäß einem der Ansprüche 1 bis 3 oder ein Polymer, das durch Polymerisieren der Verbindung gebildet wird.
  7. Verbindung, die durch die folgende allgemeine Formel (I-A) dargestellt wird:
    Figure imgb0069
     wobei:
    Ar1 und Ar2 jeweils unabhängig voneinander eine Einfachbindung, einen aromatischen Ring mit 5 bis 14 Kohlenstoffatomen oder eine Biphenylgruppe darstellen, unter der Voraussetzung, daß wenigstens eines von Ar1 und Ar2 einen Naphthalinring und eine Biphenylgruppe darstellen, die einen Substituenten aufweisen können;
    -Ar2-P4 die 4-Position oder 5-Position eines Thiophenrings substituiert;
    P3 eine lineare, verzweigte oder cyclische Alkylgruppe mit 1 bis 20 Kohlenstoffatomen darstellt, wobei eines oder mehrere der -CH2- in der Alkylgruppe durch -O-, -CO-, -NR1- ersetzt sein können, indem R1 eine lineare, verzweigte oder cyclische Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, -CH=CH- oder -C≡C- darstellt, vorausgesetzt, daß Heteroatome nicht benachbart zueinander angeordnet sind, und die Alkylgruppe kann einen Substituenten aufweisen, der aus den Atomen ausgewählt aus C, H, O, N, S und einem Halogenatom besteht;
    P4 -P4'-P6 darstellt,
    wobei:
    P6 eine lineare, verzweigte oder cyclische Alkylgruppe mit 1 bis 20 Kohlenstoffatomen darstellt, wobei eines oder mehrere der -CH2- in der Alkylgruppe durch -O-, -CO-, -CH=CH- oder -C=C- ersetzt sein können, vorausgesetzt, daß Heteroatome nicht benachbart zueinander angeordnet sind, und die Alkylgruppe kann einen Substituenten aufweisen, der aus den Atomen ausgewählt aus C, H, 0, N, S und einem Halogenatom besteht; und
    P4' eine divalente elektronenanziehende Gruppe darstellt, die ausgewählt ist aus der Gruppe bestehend aus einer Estergruppe (-COO-), einer Sulfonylgruppe (-SO2-) und einer Sulfoxygruppe (-SO3-);
    D1 eines ausgewählt aus der Gruppe bestehend aus einem Sauerstoffatom (-O-), einem Schwefelatom (-S-) und -NP5- darstellt, in dem P5 ein Wasserstoffatom oder eine lineare, verzweigte oder cyclische Alkylgruppe mit 1 bis 20 Kohlenstoffatomen darstellt, wobei eines oder mehrere der -CH2- in der Alkylgruppe durch -O-, -CO-, -CH=CH- oder -C≡C- ersetzt sein können, vorausgesetzt, daß Heteroatome nicht benachbart zueinander angeordnet sind, und die Alkylgruppe kann einen Substituenten aufweisen, der aus den Atomen ausgewählt aus C, H, O, N, S und einem Halogenatom besteht, und P5 kann unabhängig von P3 sein oder unter Ausbildung eines Rings an P3 gebunden sein; und
    der Thiophenring einen Substituenten aufweisen kann.
  8. Verbindung gemäß Anspruch 7, wobei:
    Ar1 eine 1,4-Phenylengruppe ist und Ar2 eine 2,6-Naphthalingruppe ist; oder
    Ar1 eine 2,6-Naphthalingruppe ist und Ar2 eine 1,4-Phenylengruppe ist.
  9. Verbindung gemäß Anspruch 7 oder 8, wobei P3 und P5 jeweils unabhängig voneinander eine lineare, verzweigte oder cyclische Alkylgruppe mit 1 bis 20 Kohlenstoffatomen darstellen.
  10. Optisches Element umfassend die Verbindung gemäß einem der Ansprüche 7 bis 9 oder ein Polymer dieser Verbindung.
  11. Nichtlineares optisches Material umfassend als wenigstens einen Bestandteil die Verbindung gemäß einem der Ansprüche 7 bis 9 oder ein Polymer, das durch Polymerisieren der Verbindung gebildet wird.
  12. Elektrooptisches Material umfassend als wenigstens einen Bestandteil die Verbindung gemäß einem der Ansprüche 7 bis 9 oder ein Polymer, das durch Polymerisieren der Verbindung gebildet wird.
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